Compositions containing chlorofluoroolefins or fluoroolefins

ABSTRACT

Compositions and methods based on the use of fluoroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon double bond, such as HFO-1214, HFO-HFO-1233, or HFO-1354 having properties highly beneficial in foaming and blowing agent applications, articles and methods.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 15/355,649,filed Nov. 18, 2016 (now allowed), which application is a division ofU.S. application Ser. No. 14/643,500, filed Mar. 10, 2015 (now U.S. Pat.No. 9,586,072, issued Mar. 7, 2017), which application is a division ofU.S. application Ser. No. 14/298,526, filed Jun. 6, 2014, (now U.S. Pat.No. 8,974,690, issued Mar. 10, 2015), which application is acontinuation of U.S. application Ser. No. 13/862,517, filed Apr. 15,2013, (now U.S. Pat. No. 9,095,737, issued Aug. 4, 2015), which is adivisional of U.S. application Ser. No. 12/368,094, filed Feb. 9, 2009(now U.S. Pat. No. 7,985,299, issued Jul. 26, 2011); which in turn is adivisional of U.S. application Ser. No. 11/223,447, filed Sep. 8, 2005(now U.S. Pat. No. 7,674,756, issued Mar. 9, 2010), which in turn is acontinuation-in-part of U.S. application Ser. No. 10/700,696, filed Nov.4, 2003, (now abandoned), all of which are incorporated herein byreference.

FIELD OF THE INVENTION

This invention relates to compositions and systems having utility innumerous situations, including particular solvent cleaning systems, aswell as refrigerant lubricants and/or compatibilizing agents, and tomethods which utilize such compositions and systems, More particularly,the present invention in preferred aspects is directed to solvents,blowing agents, heat transfer fluids and compatibilizing agentscomprising multi-fluorinated olefins.

BACKGROUND OF THE INVENTION

Solvent compositions are in widespread use throughout the world and in awide variety of industrial applications. Certain fluorocarbons have beenpreferred components in solvent cleaning systems for many years.Trichlorotrifluoroethane has been one of the most widely usedfluorocarbon solvents in recent years because it is generally effectiveas a solvent for many greases, oils, waxes and the like, and hastherefore found widespread use for cleaning electric motors,compressors, heavy metal parts, delicate precision metal parts, printedcircuit boards, gyroscopes, guidance systems, aerospace and missilehardware, aluminum parts and the like. Furthermore,trichlorotrifluoroethane is advantageous because it is nontoxic andnonflammable. Trichlorotrifluoroethane has two isomers: 1,12-trichloro-1 2,2-trifluoroethane (known in the art as CFC-113) and1,1,1-trichloro-2,2,2-trifluoroethane (known in the art as CFC-113a).

Concern has increased in recent years about potential damage to theearth's ozone layer, and certain chlorine-based compounds have beenidentified as particularly problematic in this regard. CFC-113 ischemically stable and therefore has a relatively long life in thestraposphere, and since the use CFC-113 as a solvent will frequentlyresult in its release into the environment, it will frequently reach thestratosphere. In the stratosphere, CFC-113 gives rise to photolysisunder the influence of sun light to generate chlorine radicals. The thusgenerated chlorine radicals combine with ozone, resulting in ozonedepletion. Accordingly, the use of organic chlorine-based compounds suchas CFCs has been severely restricted in many countries of the world bygovernmental regulation. Because CFC-113 has a high ozone destructionpotential, a need has risen to replace it, and other compounds whichexhibit similar environmentally detrimental properties.

In response to the need for stratospherically safe materials,substitutes have been developed and continue to be developed. ResearchDisclosure 14623 (June 1978) reports that1,1-dichloro-2,2,2-trifiuoroethane (HCFC-123) is a useful solvent fordegreasing and defluxing substrates. In the EPA “Findings of theChlorofluorocarbon Chemical Substitutes International Committee”,EPA-600/9-88-009 (April 1988), it was reported on pages C-22 and C-23that HCFC-123 and 1-fluoro-1,1-dichloroethane (HCFC-141b) have potentialas replacements for CFC-113 as cleaning agents. Otherhydrochlorofluorocarbon alkanes (HCFC alkanes) have been developed aspotential replacements for CFC-113, including for example1,1-dichloro-2,2,2-trifluoroethane (HCFC-123),1-fluoro-1,1-dichloroethane (HCFC-141b),1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) and1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb).

The preparation and use of fluorinated higher alkenes, that isfluorine-substituted alkenes having at least five carbon atoms, is knownFor example, U.S. Pat. No. 4,788,352—Smutny is directed to productiontri-fluorinated C₅ to C₇ compounds having at least some degree ofunsaturation. Such higher olefins are identified as being known to haveutility as refrigerants, pesticides, dielectric fluids, heat transferfluids, solvents, and intermediates in various chemical reactions. (Seecolumn I lines 11-22).

However, while many of the hydrochlorofluorocarbons described heretoforemay have substantial solvent power with respect to certain oils andfats, many also have certain disadvantages. For example, some of thesecompounds may tend to attack substrates, particularly general-purposeplastics such as acrylic resins and ABS resins. Furthermore, the higherolefinic compounds described in Smutny may also be undesirable incertain applications because of the potential level of toxicity of suchcompounds which may arise as a result of their activity as pesticides.Also, such compounds may not be sufficiently volatile to act aseffective solvents in certain vapor degreasing operations, and therelatively low vapor pressure of such compounds may make it difficult toremove the solvent composition from the parts being cleaned.

Flammability is another important property for many applications. Thatis, it is considered either important or essential in many applications,including particularly in solvent cleaning applications, to usecompositions which are non-flammable. Thus, it is frequently beneficialto use in such compositions compounds which are nonflammable. As usedherein, the term ‘nonflammable” refers to compounds or compositionswhich do not exhibit a flashpoint as measured by one of the standardflash point methods, for example ASTM-1310-86 ‘Flash point of liquids bytag Open-cup apparatus”. Unfortunately, many HFC's which might otherwisebe desirable for use in solvent compositions are not nonflammable. Forexample, the fluoroalkane pentafluorobutane (HFC-365) is flammable andtherefore not viable for use in many applications.

In many applications it is also highly desirable for solventcompositions to be relatively stable, that is, to be relativelyresistant to possible chemical changes during storage and use.Applicants have come to recognize that CFC-113 is deficient in thisregard because it tends to hydrolyze and form HCl. Furthermore, thisproblem is worsened because metal, which is typically present during anysolvent cleaning operations, acts as a catalyst and causes thehydrolysis of CFC-113 to increase dramatically:

Applicants have thus come to appreciate a need for solvent compositionsthat are potentially useful in numerous applications, includingdegreasing applications, precision cleaning and electronics cleaningapplications, dry cleaning applications, solvent etching applications,as a solvent in aerosols or other sprayable compositions, as carriersolvents for depositing lubricants and release agents and other solventor surface treatment applications.

SUMMARY OF THE INVENTION

Applicants have found that the above-noted and other needs can besatisfied, and many of the above-noted deficiencies and others can beovercome, by compositions comprising a compound having Formula I asfollows:

XCF_(z)R_(3-z)  (I)

where X is a C₂ or a C₃ unsaturated, chlorine and/or fluorinesubstituted alkyl group, each R is independently Cl, F, Br, I or H, andz is 1 to 3, preferably at least 2 and even more preferably at least 3.As used herein, the term “chlorine and/or fluorine substituted” means atleast one chlorine and/or at least one fluorine substituent on the alkylgroup X.

Applicants have also discovered methods and systems for removingcontaminants from a product, part, component, substrate, or any otherarticle or portion thereof by applying to the article a compositioncontaining a compound in accordance with Formula I. For the purposes ofconvenience, the term “article” is used herein to refer to all suchproducts, parts, components, substrates, and the like and is furtherintended to refer to any surface or portion thereof. Furthermore, theterm “contaminant” is intended to refer to any unwanted material orsubstance present on the article, even if such substance is placed onthe article intentionally. For example, in the manufacture ofsemiconductor devices it is common to deposit a photoresist materialonto a substrate to form a mask for the etching operation and tosubsequently remove the photoresist material from the substrate. Theterm “contaminant” as used herein is intended to cover and encompasssuch a photo resist material.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The Compositions

The present invention is directed to compositions comprising at leastone fluoroalkene containing from 3 to 4 carbon atoms and at least onecarbon-carbon double bond. The fluoroalkene compounds of the presentinvention are sometimes referred to herein for the purpose ofconvenience as hydrofluoro-olefins or “HFOs” if they contain at leastone fluorine and at least one hydrogen. It is intended that the term HFOalso encompasses for example such compounds that also contain othersubstituents, such chlorine. Although it is contemplated that the HFOsof the present invention may contain two carbon—carbon double bonds,such compounds at the present time are not considered to be preferred.

The present compositions comprise one or more compounds in accordancewith Formula 1. In preferred embodiments, the compositions includecompounds of Formula II below

where each R is independently Cl, F, Br, 1 or H, wherein at least oneRon an unsaturated carbon is chlorine and/or fluorine,

-   -   R′ is (CR—₂)_(n)Y,    -   Y is CRF₂    -   and n is 0 or 1.

In highly preferred embodiments, Y is CF₃ and at least twounsaturatedcarbons have a chlorine substituent.

It is contemplated that all such compounds as identified above areadaptable for use in certain aspects of the present invention. Thepreferred compound(s) in accordance with the compositions and methods ofthe present invention preferably exhibit one or more, and preferablyall, of the following properties: chemical stability; no substantialozone depleting potential (ODP); relatively high degree of miscibilitywith common contaminants, particularly mineral oil and/or silicone oil;low or no flammability; low or no toxicity; and low or no global warmingpotential (GWP).

The preferred compounds for use in the present compositions have beenfound to possess at once several of these desirable beneficialproperties. More specifically, the preferred compounds have: nosubstantial ozone depletion potential, preferably an ODP of not greaterthan about 0.5 and even more preferably of not greater than about 0.25,most preferably of not greater than about 0.1; a GWP of not greater thanabout 150, and even more preferably of not greater than about 50. Inmany of the preferred embodiments, the compound of the present inventionhas a normal boiling point of from about 20° C. to about 70° C., andeven more preferably of from about 45° C. to about 60° C., and even morepreferably from about 50° C. to about 60° C. It is also generallypreferred that the compound(s) have no flash point as measured by one ofthe standard flash point methods, for example ASTM-1310-86 “Rash pointof liquids by tag Open-cup apparatus” and an atmospheric lifetime of notgreater than about 100 days and even more preferably of not greaterabout 50 days. Also, the preferred compound(s) are miscible with greaterthan 20% by weight of mineral oil and/or silicone oil, more preferablyin a weight ratio in the range of at least about 80:20 to about 20:80,and even more preferably in substantially all proportions.

Preferred compounds of the present invention exhibit a relatively lowtoxicity value. Applicants have found that one compound within the scopeof the present invention, namely HF0-1223xd(1,2-dichloro-3,3,3-trifluoropropene), is generally not desirable foruse in connection with applications in which low or no toxicity isimportant. In certain preferred embodiments, therefore, the presentcomposition and methods do not include any substantial amount ofHFC-1223xd, and more preferably comprise one or more compounds withinFormula I or Formula II which have an acute toxicity level, ashereinafter described, substantially less than, and preferably at leastabout 30 relative percent less than, HF0-1223xd.

As used herein, ODP is defined in the “Scientific Assessment of OzoneDepletion, 2002”, a report of the World Meteorological association,incorporated here by reference. As used herein, GWP is defined relativeto that of carbon dioxide and over a 100 year time horizon, and definedin the same reference as for the ODP mentioned above. As used herein,miscibility is measured in accordance with visual evaluation of phaseformation or separation when two liquids are mixed together, as is knownto those skilled in the art.

The compositions of the present invention thus generally possessproperties and characteristics that are highly desirable for use inconnection with many different applications, including many differenttypes of cleaning and contaminant removal applications.

Cleaning Compositions

One of the most important characteristic of the present invention as itrelates to cleaning applications is that the present compositions havebeen found to have a high level of solvent power for many commoncontaminants and residues while at the same time not having a highdegree of acute toxicity, as measured by exposure to mice and rats.Preliminary toxicity for certain compounds within the scope of thosedescribed by Formula I above was published in Anesthesiology, Vol 14, pp466-472, 1953.

In certain preferred embodiments, the solvent cleaning compositioncomprises a compound of Formula I or II having an acute toxicity levelsubstantially less than, and preferably at least about 30 relativepercent less than, the toxicity level of HFO-1223xd. In certainpreferred embodiments, the solvent compositions of the present inventioncomprise, and preferably comprise at least about 50 percent by weightof, one or more substituted or unsubstituted C₃-C₄ tetrafluoroalkenes.In certain highly preferred embodiments, the solvent compositions of thepresent invention comprise dichloro-tetrafluoro-propenes, such asisomers of HFO-1214; chloro-trifluoro-propenes, such as isomers ofHFO-1233; and tetrafluorobutenes, such as isomers of FIFO-1354. Specificexamples of these compounds include 1,2-dichloro-1,33,3-tetrafluoro-1-propene (CF₃—CCl═CClF);1-chloro-3,3,3-trifluoro-1-propene (CF₃₋CH═CHCl);2-chloro-3,3,3-trifluoro-1-propene (CF₃—CH═CHCl);2,4,4,4-tetrafluoro-1-butene (CF₃—CH₂—CH═CH₂);1,1,1,3-tetrafluoro-2-butene (CH₃—CH═CF—CH₃); and1,1,3,3-tetrafluoro-1-butene (CF₂═CH—CF₂—CH₃). In certain preferredembodiments, solvents comprise a mixture of1-chloro-3,3,3-trifluoro-1-propene and2-chloro-3,3,3-trifluoro-1-propene or a mixture of one or more of 24,4,4-tetrafluoro-1-butene; 1,1,1,3-tetrafluoro-2-butene; and1,1,3,3-tetrafluoro-1-butene.

One aspect of the present intervention thus provides surface treatmentcompositions comprising at least a substantial amount of at least onecompound in accordance with Formula 1, more preferably Formula II, andeven more preferably a compound in accordance with Formula I or IIhaving an acute toxicity level substantially less than, and preferablyat least about 30 relative percent less than, the toxicity level ofHFO-1223xd. In certain embodiments, the present treatment compositionsconsist essentially of, and in some preferred embodiments consist of,one or more compounds in accordance with Formula I, more preferablyFormula 11, and even more preferably a compound in accordance withFormula. I or II having an acute toxicity level substantially less than,and preferably at least about 30 relative percent less than, thetoxicity level of HFO-1223xd. However, it is also contemplated that inmany embodiments the composition will include other components inaddition to the above-noted compounds. For example, it is contemplatedthat in certain embodiments the surface treating compositions mayinclude co-solvents, anticorrosive agents, surfactants, stabilizers,inhibitors and other adjuvants which assist with or enhance thefunctionality of the composition. Examples of co-solvents includelinear, branched and cyclic hydrocarbons, halocarbons, includingchlorinated and brominated compounds, alcohols, such as methanol,ethanol, propanol, isopropanol, butanol, etc., ketones, esters, ethersand acetals. Examples of stabilizers include nitroalkanes, epoxy alkanesand phosphite esters. Some of these form azeotrope—like compositionswith HFO-1214, HFO-1233, and/or HFO-1354.

Although it is contemplated that the compositions of the presentinvention may include the compounds of the present invention in widelyranging amounts, it is generally preferred that the solvent cleaningcompositions of the present invention comprise a compound in accordancewith Formula I, and even more preferably Formula II, in an amount thatis at least about 10% by weight, and even more preferably at least about30% by weight, of the composition.

In certain embodiments the present compositions are well adapted forused in the form of an aerosol and/or a sprayable composition, and insuch embodiments it is contemplated that the present compositions mayhave one or more additives designed for this use, such as propellants,atomizing agents and the like.

Heat Transfer Compositions

it is contemplated that when the compositions of the present inventionare used in heat transfer applications, such compositions may includethe compounds of the present invention in widely ranging amounts. It isgenerally preferred, however, that the heat transfer compositions of thepresent invention, especially the refrigerant compositions of thepresent invention, comprise compound(s) in accordance with Formula I,more preferably Formula II and even more preferably a compound inaccordance with Formula I or II having an acute toxicity levelsubstantially less than, and preferably at least about 30 relativepercent less than, the toxicity level of HFO-1223xd, in an amount thatis at least about 50% by weight, and even more preferably at least about70% by weight, of the composition.

The heat transfer compositions of the present invention may includeother components for the purpose of enhancing or providing certainfunctionality to the composition, or in some cases to reduce the cost ofthe composition. For example, refrigerant compositions according to thepresent invention, especially those used in vapor compression systems,include a lubricant, generally in amounts of from about 30 to about 50percent by weight of the composition. Furthermore, the presentcompositions may also include a compatibilizer, such as propane, for thepurpose of aiding compatibility and/or solubility of the lubricant. Suchcompatibilizers, including propane, butanes and pentanes, are preferablypresent in amounts of from about 0.5 to about 5 percent by weight of thecomposition. Combinations of surfactants and solubilizing agents mayalso be added to the present compositions to aid oil solubility, asdisclosed by U.S. Pat. No. 6,516,837, the disclosure of which isincorporated by reference. Commonly used refrigeration lubricants suchas Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs) that are usedin refrigeration machinery with hydrofluorocarbon (HFC) refrigerants maybe used with the refrigerant compositions of the present invention.

For compatibilizing compositions of the present invention, it may bepreferred to include in such compositions co-solvents, anticorrosiveagents, surfactants, stabilizers and other adjuvants which assist withor enhance the functionality of the composition. For preferredcompatibilizing compositions of the present invention, compound(s) inaccordance with Formula I, more preferably Formula II, and even morepreferably a compound in accordance with Formula I or II having an acutetoxicity level substantially less than, and preferably at least about 30relative percent less than, the toxicity level of HF0-1223xd, arepresent in an amount that is at least about 25% by weight, and even morepreferably at least about 50% by weight, of the composition.

Blowing Agents, Foams and Foamable Compositions

Blowing agents may also comprise or constitute one or more of thepresent compositions. As mentioned above, the compositions of thepresent invention may include the compounds of the present invention inwidely ranging amounts. It is generally preferred, however, that forpreferred compositions for use as blowing agents in accordance with thepresent invention, compound(s) in accordance with Formula I, morepreferably Formula. II, and even more preferably a compound inaccordance with Formula I or II having an acute toxicity levelsubstantially less than, and preferably at least about 30 relativepercent less than, the toxicity level of HFO-1223xd, are present in anamount that is at least about 5°/0 by weight, and even more preferablyat least about 15% by weight, of the composition.

In other embodiments, the invention provides foamable compositions, andpreferably polyurethane, polyisocyanurate and extruded thermoplasticfoam compositions, prepared using the compositions of the presentinvention. In such foam embodiments, one or more of the presentcompositions are included as or part of a blowing agent in a foamablecomposition, which composition preferably includes one or moreadditional components capable of reacting and/or foaming under theproper conditions to form a foam or cellular structure, as is well knownin the art. The invention also relates to foam, and preferably closedcell foam, prepared from a polymer foam formulation containing a blowingagent comprising the compositions of the invention, In yet otherembodiments, the invention provides a foamable composition comprisingthermoplastic foams, such as polystyrene and polyethylene (PE),preferably low density PE.

In certain preferred embodiments, dispersing agents, cell stabilizers,surfactants and other additives may also be incorporated into theblowing agent compositions of the present invention. Surfactants areoptionally but preferably added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458, each of which is incorporated herein byreference. Other optional additives for the blowing agent mixture mayinclude flame retardants such as tri(2-chloroethyl)phosphate,tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,tri(1,3-dichloropropyl) phosphate, diammonium phosphate, varioushalogenated aromatic compounds, antimony oxide, aluminum trihydrate,polyvinyl chloride, and the like.

Methods and Systems

The compositions of the present invention are useful in connection withnumerous methods and systems, including: as a solvent in solventcleaning methods, particularly vapor degreasing; heat transfer fluids inmethods and systems for transferring heat, such as refrigerants used inrefrigeration, air conditioning and heat pump systems; as a component inmethods and systems for extinguishing and suppressing fire; as anadditive to reduce the flammability of fluids; and as a componentinvolved in the formation of foam, foam premixes, foam products andblowing agents for foams.

Cleaning Methods

The contaminant removal aspects of the present invention comprisecontacting the contaminated article with at least one compound of thepresent invention. In preferred embodiments, the methods compriseapplying a solvent composition of the present invention to the articlecontaining the contaminant, with vapor degreasing and solvent cleaningmethods being particularly preferred for certain applications,especially those especially intricate parts and difficult to removesoils. As those skilled in the art will appreciate, the present methodshave applicability to a wide variety of different cleaning and residueremoval techniques, and all such techniques are within the broad scopeof the present invention.

Preferred methods of the present invention comprise applying the presentcomposition to the article, with vapor degreasing and solvent cleaningmethods being particularly preferred for certain applications,especially those involving intricate parts and difficult to removesoils. Preferred vapor degreasing and solvent cleaning methods consistof exposing an article, preferably at room-temperature, to the vapors ofa boiling solvent. Vapors condensing on the object have the advantage ofproviding a relatively clean, distilled solvent to wash away grease orother contamination. Such processes thus have an additional advantage inthat final evaporation of the present solvent composition from theobject leaves behind relatively little residue as compared to the casewhere the object is simply washed in liquid solvent.

For applications in which the article includes contaminants that aredifficult to remove, it is preferred that the present methods involveraising the temperature of the solvent composition of the presentinvention above ambient or to any other temperature that is effective insuch application to substantially improve the cleaning action of thesolvent. Such processes are also generally preferred for large volumeassembly line operations where the cleaning of article, particularlymetal parts and assemblies, must be done efficiently and quickly.

In preferred embodiments, the cleaning methods of the present inventioncomprise immersing the article to be cleaned in liquid solvent at anelevated temperature, and even more preferably at about the boilingpoint of the solvent. In such operations, this step preferably removes asubstantial amount, and even more preferably a major portion, of thetarget contaminant from the article. This step is then preferablyfollowed by immersing the article in solvent, preferably freshlydistilled solvent, which is at a temperature below the temperature ofthe liquid solvent in the preceding immersion step, preferably at aboutambient or room temperature. The preferred methods also include the stepof then contacting the article with relatively hot vapor of the presentsolvent composition, preferably by exposing the article to solventvapors rising from the hot/boiling solvent associated with the firstmentioned immersion step. This preferably results in condensation of thesolvent vapor on the article. In certain preferred embodiments, thearticle may be sprayed with distilled solvent before final rinsing.

It is contemplated that numerous varieties and types of vapor degreasingequipment are adaptable for use in connection with the present methods.One example of such equipment and its operation is disclosed bySherliker et al. in U.S. Pat. No. 3,085,918, which is incorporatedherein by reference. The equipment disclosed in Sherliker et al includesa boiling sump for containing a solvent composition, a clean sump forcontaining distilled solvent, a water separator, and other ancillaryequipment.

The present cleaning methods may also comprise cold cleaning in whichthe contaminated article is either immersed in the fluid composition ofthe present invention under ambient or room temperature conditions orwiped under such conditions with rags or similar objects soaked insolvents. In addition, the present methods may comprise or consistessentially of applying the present composition to the article byspraying the composition onto the article.

Heat Transfer Methods

The preferred heat transfer methods generally comprise providing acomposition of the present invention and causing heat to be transferredto or from the composition changing the phase of the composition. Forexample, the present methods provide cooling by absorbing heat from afluid or article, preferably by evaporating the present refrigerantcomposition in the vicinity of the body or fluid to be cooled to producevapor comprising the present composition. Preferably the methods includethe further step of compressing the refrigerant vapor, usually with acompressor or similar equipment to produce vapor of the presentcomposition at a relatively elevated pressure. Generally, the step ofcompressing the vapor results in the addition of heat to the vapor, thuscausing an increase in the temperature of the relatively high pressurevapor. Preferably, the present methods include removing from thisrelatively high temperature, high pressure vapor at least a portion ofthe heat added by the evaporation and compression steps. The heatremoval step preferably includes condensing the high temperature, highpressure vapor while the vapor is in a relatively high pressurecondition to produce a relatively high pressure liquid comprising acomposition of the present invention. This relatively high pressureliquid preferably then undergoes a nominally isoenthalpic reduction inpressure to produce a relatively low temperature, low pressure liquid.In such embodiments, it is this reduced temperature refrigerant liquidwhich is then vaporized by heat transferred from the body or fluid to becooled.

In another process embodiment of the invention, the compositions of theinvention may be used in a method for producing heating which comprisescondensing a refrigerant comprising the compositions in the vicinity ofa liquid or body to be heated. Such methods, as mentioned hereinbefore,frequently are reverse cycles to the refrigeration cycle describedabove.

The present invention also includes the use of the present compositionsin connection with heat transfer methods comprising adding and/orremoving sensible heat from the present compositions, preferably bybringing the present composition into convective or conductive heattransfer relationship with an article or fluid to be heated orcooled_Such contact is most preferably indirect contact, such as wouldoccur through the present composition being exposed to a heat transfersurface located on one side of a fluid transfer barrier. Typically, thearticle or fluid to be cooled or heated is located on the other side ofsuch a barrier but in contact with a surface that is thermodynamicallycoupled to the heat transfer surface in contact with the composition ofthe present invention. Finned tube heat exchangers are common example ofsuch an apparatus, which also may be used in connection with phasechange heat transfer as discussed above.

Flammability Reduction Methods

According to certain other preferred embodiments, the present inventionprovides methods for reducing the flammability of fluids, said methodscomprising adding a compound or composition of the present invention tosaid fluid. The flammability associated with any of a wide range ofotherwise flammable fluids may be reduced according to the presentinvention. For example, the flammability associated with fluids such asethylene oxide, flammable hydrofluorocarbons and hydrocarbons,including: HFC-365, hexane, octane, and the like can be reducedaccording to the present invention. For the purposes of the presentinvention, a flammable fluid may be any fluid exhibiting flammabilityranges in air as measured via any standard conventional test method,such as ASTM E-681, and the like.

Any suitable amounts of the present compounds or compositions may beadded to reduce flammability of a fluid according to the presentinvention. As will be recognized by those of skill in the art, theamount added will depend, at least in part, on the degree to which thesubject fluid is flammable and the degree to which it is desired toreduce the flammability thereof. In certain preferred embodiments, theamount of compound or composition added to the flammable fluid iseffective to render the resulting fluid substantially non-flammable.

Flame Suppression Methods

The present invention further provides methods of suppressing a flame,said methods comprising contacting a flame with a fluid comprising acompound or composition of the present invention. Any suitable methodsfor contacting the flame with the present composition may be used. Forexample, a composition of the present invention may be sprayed, poured,and the like onto the flame, or at least a portion of the flame may beimmersed in the composition. In light of the teachings herein, those ofskill in the art will be readily able to adapt a variety of conventionalapparatus and methods of flame suppression for use in the presentinvention.

Foam Blowing Methods

One embodiment of the present invention relates to methods of formingfoams, and preferably polyurethane and polyisocyanurate foams. Themethods generally comprise providing a blowing agent composition of thepresent inventions, adding (directly or indirectly) the blowing agentcomposition to a foamable composition, and reacting the foamablecomposition under the conditions effective to form a foam or cellularstructure, as is well known in the art. Any of the methods well known inthe art, such as those described in “Polyurethanes Chemistry andTechnology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley andSons, New York, N.Y., which is incorporated herein by reference, may beused or adapted for use in accordance with the foam embodiments of thepresent invention. In general, such preferred methods comprise preparingpolyurethane or polyisocyanurate foams by combining an isocyanate, apolyol or mixture of polyols, a blowing agent or mixture of blowingagents comprising one or more of the present compositions, and othermaterials such as catalysts, surfactants, and optionally, flameretardants, colorants, or other additives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the “B” component.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, and even otherpolyols can be added as a third stream to the mix head or reaction site.Most preferably, however, they are all incorporated into one B-componentas described above.

It is also possible to produce thermoplastic foams using thecompositions of the invention. For example, conventional polystyrene andpolyethylene formulations may be combined with the compositions in aconventional manner to produce rigid foams.

What is claimed:
 1. A. composition comprising: (a) mineral oil; (b) atleast about 10% by weight of one or more compounds in accordance withFormula II:

where R′ is —CF₃ and each R is independently Cl, F or H, provided thatat least one R on the unsaturated terminal carbon is chlorine, andwherein (i) said one or more compounds of Formula II include nosubstantial amount of 1,2-dichloro-3,3,3-trifluoropropene, and (II) theacute toxicity level of said one or more compounds of Formula. I! is atleast 30 relative percent less than the acute toxicity level of1,2-dichloro-3,3,3-trifluoropropene,1-chloro-3,3,3-trifluoro-1-propene(CF₃—CH═CHCl).
 2. The composition of claim 1 wherein said one or morecompounds in accordance with Formula II consist essentially of1-chloro-3,3,3-trifluoro-1-propene (CF₃—CH═CHCl.)
 3. The composition ofclaim 2 wherein said composition consists essentially of said mineraloil and said 1-chloro-3,3,3-trifluoro-1-propene.
 4. The composition ofclaim 3 wherein said 1-chloro-3,3,3-trifluoro-1-propene is present inthe composition n amount of at least about 20% by weight and saidmineral oil is present in the composition in an amount of at least about20%,
 5. The composition of claim 3 wherein said1-chloro-3.3.3-trifluoro-1-propene is present in the composition amountof at least about 30% by weight.
 6. The composition of claim 3 whereinsaid 1-chloro-3,3,3-trifluoro-1-propene is present in the composition inamount of at least about 50% by weight.
 7. The composition of claim 2wherein said mineral oil is present in the composition in an amount ofat least about 20%.
 8. The composition of claim 2 wherein said1-chloro-3,3,3-trifluoro-1-propene is present in the composition inamount of at least about 70% by weight.
 9. The composition of claim 8wherein said composition consists essentially of said mineral oil andsaid 1-chloro-3,3,3-trifluoro-1-propene.
 10. The composition of claim 2wherein said wherein said 1-chloro-3,3,3-trifluoro-1-propene:mineral oilweight ratio is from about 80:20 to about 20:80.
 11. The composition ofclaim 2 wherein said 1-chloro-3,3,3-trifluoro-1-propene and said mineraloil are miscible.
 12. The composition of claim 11 wherein said1-chloro-3,3,3-trifluoro-1-propene is present in the composition inamount of at least about 50% by weight.
 13. The composition of claim 2wherein said 1-chloro-3,3,3-trifluoro-1-propene and said mineral oil aremiscible in substantially all proportions.
 14. The composition of claim10 wherein said 1-chloro-3,3,3-trifluoro-1-propene and said mineral oilare miscible in substantially all proportions.
 15. A heat transfercomposition comprising: (a) at least about 10% by weight of one or morecompounds in accordance with Formula II:

where R′ is —CF₃ and each R is independently Cl, F or H, provided thatat least one R on the unsaturated terminal carbon is chlorine, andwherein (i) said one or more compounds of Formula II include nosubstantial amount of 1,2-dichloro-3,3,3-trifliuoropropene, and (ii) theacute toxicity level of said one or more compounds of Formula. II is atleast 30 relative percent less than the acute toxicity level of1,2-dichloro-3,3,3-trifluoropropene: and (b) at least one additionalcomponent.
 16. The heat transfer composition of claim 15 wherein said atleast one additional component comprises at least one lubricant andwherein said at least one or more compounds of Formula II consistessentially of 1-chloro-3,3,3-trifluoro-1-propene (CF₃—CH═CHCl).
 17. Anair conditioning system comprising a heat transfer compositioncomprising: (a) at least about 50% by weight of one or more compounds inaccordance with Formula II:

where, R. and each R is independently Cl, F or H, provided that at leastone R on the unsaturated terminal carbon is chlorine: and wherein (i)said one or more compounds of Formula II include no substantial amountof 1,2-dichloro-3,3,34 iflioropropene, and (ii) the acute toxicity levelof said one or more compounds of Formula II is at least 30 relativepercent less than the acute toxicity level of 1,2-dichloro-3,33-trifluoropropene: and (b) at least one additional component comprisinglubricant.
 18. The air conditioning system of claim 17 wherein said oneor more compounds in accordance with Formula II consists essentially of1-chloro-3,3,3-trifluoro-1-propene (CF₃—CH═CHCl).